The Ti-ZSM-5 zeolite samples were successfully synthesized via gas-solid method with B-ZSM-5 zeolite prepared by modified hydrothermal synthesis as precursor. The samples were characterized by XRD, FT-IR, UV-Vis, XRF, SEM, ICP-AES and MAS NMR, and their catalytic performance for hydroxylation of phenol was investigated. The results showed that the crystallization at lower temperature during the synthesis of BZSM-5 was advantageous to get smaller crystal size and the Ti-ZSM-5 samples prepared by using B-ZSM-5 with smaller crystal size as precursor showed better performance for hydroxylation of phenol. Under the reaction conditions of n (PhOH) In (H2O2) = 3, n (Me2CO) In (PhOH) = 2.7, m (cat) /m (PhOH) = 5 %, T = 353 K and t = 6 h, the phenol conversion was over 20 %.